Phthalocyanine pigment compositions



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UNITED STATES PATENT OFFICE PHTHALOCYANINE PIGMENT COMPOSITIONS Vito A. Giambalvo, Somervill, N. J., assignor t5 Interchemical Corporation, New York, N; Y.-, a;

corporation of Ohio N Drawing. Application February 23 1946; Serial N0. 649,757

8 Claims.

This invention relates to the production of phthalocyanine pigments and their use in liquid coating compositions such as paints, lacquersand enamels, and aims to provide more useful pigments of this general class.

Despite their remarkable color and brilliancy, in addition to their. valuable properties of heat, light and chemical resistance, phthalocyanines have found limited application in the protective white will float to the surface, giving an off-color.

Or were a phthalocyanine blue and a yellow ground into a green enamel, the blue and the yellow will separate, giving off color.

It is the object of this invention to prepare a phthalocyanine pigment which will be stably dispersed in a liquid composition over a relmtively long time, in order to overcome the loss in shade and strength which results when combined with other pigments.

I have found that phthalocyanine mono-sulphonic acid, prepared by treating phthalocyanines with sulphonating agents, such as hot concentrated sulphuric or cold fumingsulphuric acid, when admixed in quantities of the order of 5% or more with unsulphonated phthalocyanines, will stabilize the phthalocyanine dispersion and protect it' against flocculation in a conventional paint, lacquer and enamel. The phthalocyanine mono-sulphonic acids can be used to replace all the corresponding unsulphonated phthalocyanine; but as the percentage rises, a tendency toward gelation of the coating composition sets in with some film formingagents. Consequently, I prefer not to use above 80% of the sulphonated product in compositions such as nitrocellulose lacquers, which show tendencies toward gelation. Optimumresults are obtained the product undesirable for most coatings.

The sulphonation methodsemployed should be relatively mild; or some poly-.sulphonic acid bel-usedto replace the acid itself.

will be formed. Thus, I prefer to operate with cold fuming acid, instead of hot, as is commonly done in sulphonating. obtained with hot concentrated acid.

. The salts of the acids with various metals may When alkali metal salts are used, there is an increased tendency to water-solubility. The alkaline earth salts, however, are even less water-sensitive than the acid itself. though metals. which yield color should preferably be avoided.

(e. g. iron) The following examples are typical of the preparation of satisfactory pigments:

V Ezrample 1 '10 parts of crude.copper phthalocyanine was dissolved in parts of exactly 100.0% H2804;

in an iron sulphonator. The solution was heated slowly (over a period of eight hours) to 140 C., and immediately cooled to room temperature to arrest further sulphonation. The solution was struck in a centrifugal pump with 1000 parts of water at 60 C., pressed and washed acid-free in the conventional manner.

Metal-free phthalocyanine can be reacted in identical fashion, as shown in Example 1. Monochlor copper phthalocyanine likewise gives sim-' Example 2 A lacquer suitable for automotive use was prepared b grinding the following paste in a steel ball mill for 48' hours.

- Grams Copper phthalocyanine 240 "30% 4 sec. R. S. nitrocellulose dope 600 #15blown castor oil Dibutyl phthalate 105 Solvent-2 ethylacetate, 1 n-butyl acetate,

1 n-butanol, 6' toluene 690 Grand total I 1740' The'above paste was reduced in the following manner;

A light baby blue tint was made by letting down 20 parts of the above finished lacquer. with Similar results may be Other salts may be used, al-

' Gramsj 100 parts of any white lacquer; after standing five minutes, the blue separated from the white.

Example 3 Another lacquer on exactly the same formula as Example 2 was made, except substituting 10% of the copper phthalocyanine with copper phthalocyanine mono-sulphonic acid, as prepared in Example 1. The baby blue tint remained stable for two months without separating.

Panels were sprayed three double coats on bare metal to give solid coverings with lacquers of Example 2 and Example 3. The tint containing copper phthalocyanine sulphonic acid was brighter, and possessed 40% extra strength.

Example 4 An enamel was prepared on the following formula:

Per cent Copper phthalocyanine 12.5 Glyptal 2462 (solid) (oil-modified glycerol phthalate resin) 27.5 Toluol 39.0

Xylol 15.8 Petroleum spirits 5.2

Total 100.0

100.00 grams above paste 45.00 grams Glyptal 2462 (50% solution) 0.70 grams 24% lead nuodex, lead naphthenate type drier 0.30 grams 6% cobalt nuodex, cobalt+ naphthenate type drier The reduced paste was let down with white enamel to a baby blue tint; again the blue separated from the white, showing bad flocculation.

Example 5 An enamel on exactly the same formula as Example 4, except substituting of the copper phthalocyanine with copper phthalocyanine mono-sulphonic acid, gave a product which was non-flocculating.

Example 6 Still another enamel was prepared with the alkyd base of Example 4 but substituting a copper phthalocyanine sulphonate as in Example 1 in place of all the copper phthalocyanine of Example 4. The resultant composition was non-flocculating and a little less thixotropic than the composition of Example 4.

Example 7 Another desirable formula is:

Per cent Copper phthalocyanine sulphonated to the 15.00 grams Melmac 245-8 (50% solution) (melamine formaldehyde resin) 0.70 grams 24% lead nuodex (lead naphthenate) 0.30 grams 6% cobalt nuodex (cobalt naphthenate) Finishes based on this formulation are nonflocculating, of good working viscosity and superior weathering characteristics.

Obviously, the examples can be multiplied indefinitely. The lacquers and alkyd resin enamels shown can be replaced by other oily, oleoresinous, resinous and cellulose derivative compositions. The results observed with mixtures of white and blue are just as observable with other mixtures, and ordinary blue lacquers and enamels containing no other pigment will benefit by my treatment.

Furthermore, while I have given only one specific method of sulphonation, any other mild sulphonation may be employed, if care be taken to prevent sulphonation beyond the mono-sulphonic acid.

While the pigment treated in the above instances is copper phthalocyanine blue, other phthalocyanines which fiocculate can be similarly treated. Thus, phthalocyanine green (highly chlorinated copper phthalocyanine) fiocculates badly without the addition, and its flocculation is prevented by the use of its mono-sulphonate. Other metallic and non-metallic phthalocyanines show similar reaction.

For such subject matter as is common to my copending application Serial No. 557,217, filed October 4, 1944 (and now abandoned), and this application, I claim the benefit of the filing date thereof.

I claim:

1. A non-fiocculating liquid organic coating composition comprising a non-aqueous organic liquid coating vehicle, and a phthalocyanine pigment consisting of 5 to 40% of a compound of the class consisting of phthalocyanine mono-sulphonic acid, and its alkali earth metal salts, and 95 to 60% of unsulphonated phthalocyanine, in admixture with another pigment, the composition being characterized by the non-separation of the phthalocyanine and the other pigment.

2. A phthalocyanine pigment which is nonfiocculating in liquid nitrocellulose base coating compositions, and which is relatively free from tendencies toward gelation, consisting of 5 to 40% of a. compound of the class consisting of phthalocyanine mono-sulphonic acid and its alkali earth metal salts, and 95 to 60% of unsulphonated phthalocyanine.

3. A phthalocyanine pigment which is nonflocculating in liquid organic coating compositions, consisting of 5 to of a compound of the class consisting of phthalocyanine mono-sulphonic acid and its salts, and to 20% of unsulphonated phthalocyanine.

4. A phthalocyanine pigment which is nonfiocculating in liquid organic coating compositions, consisting of 5 to 80% copper phthalocyanine mono-sulphonic acid, and 95 to 20% of unsulphonated copper phthalocyanine.

5. A non-fiocculating liquid organic coating composition comprising a non-aqueous organic liquid coating vehicle, and a phthalocyanine pig ment consisting of 5 to 80% phthalocyanine mono-sulphonic acid, and 95 to 20% of an unsulphonated phthalocyanine.

6. A non-flocculating liquid organic coating composition comprising a non-.aqueous organic liquid coating vehicle, anda phthalocyanine pigment consisting of 5 to 80% copper phthalo: cyanine mono-sulphonic acid, and 95 to 20% of unsulphonated copper phthalocyanine.

7. A non-flocculating liquid organic coating composition comprising a non-aqueous organic 5 liquid coating vehicle, and a phthalocyanine pigment consisting of 5 to 80% of a compound of the class consisting of phthalocyanine mono-sul- 0 phonic acid, and itssalts, and 95 to 20% of an unsulphonated phthalocyanine, in admixture with another pigment, the composition being characw terized by the non-separation of the phthalocyanine and the other pigment.

8. A non-fiocculating liquid organic coating composition comprising a non-aqueous organic liquid coating vehicle, and a phthalocyanine pigment consisting of 5 to 80% copper phtha-Iocyanine mono-sulphonic acid, and 95 to 20% of unsulphonated copper phthalocyanine, in admixture with another pigment, the composition being characterized by the non-separation of the phthalocyanine and the other pigment.

VITO A. GIAMBALVO.

REFERENCES CITED The foliowing references are of record in the file of this patent:

UNITED STATES PA'IENTS Number Name Date 2,099,690 Holzach et a1 Nov. 23, 1937 2,135,633 Bienert et a1 Nov. 8, 1938 2,238,243 Black Apr. 15, 1941 2,327,472 Vesce et a1. Aug. 24, 1943 FOREIGN PATENTS Number Country Date 460,1 1! Great Britain June 20, 1936 

1. A NON-FLOCCULATING LIQUID ORGANIC COATING COMPOSITION COMPRISING A NON-AQUEOUS ORGANIC LIQUID COATING VEHICLE, AND A PHTHALOCYANINE PIGMENT CONSISTING OF 5 TO 40% OF A COMPOUND OF THE CLASS CONSISTING OF PHTHALOCYANINE MONO-SULPHONIC ACID, AND ITS ALKALI EARTH METAL SALTS, AND 95 TO 60% OF UNSULPHONATED PHTHALOCYANINE, IN ADMIXTURE WITH ANOTHER PIGMENT, THE COMPOSITION BEING CHARACTERIZED BY THE NON-SEPARATION OF THE PHTHALOCYANINE AND THE OTHER PIGMENTS. 